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20 pags., 9 figs., 1 tab. ; Biogenic very short-lived bromocarbons (VSLBr) currently represent 25% of the total stratospheric bromine loading. Owing to their much shorter lifetime compared to anthropogenic long-lived bromine (e.g. halons) and chlorine (e.g. chlorofluorocarbons), the impact of VSLBr on ozone peaks in the lowermost stratosphere, which is a key climatic and radiative atmospheric region. Here we present a modelling study of the evolution of stratospheric ozone and its chemical loss within the tropics and at mid-latitudes during the 21st century. Two different experiments are explored: considering and neglecting the additional stratospheric injection of 5 ppt biogenic bromine naturally released from the ocean. Our analysis shows that the inclusion of VSLBr results in a realistic stratospheric bromine loading and improves the agreement between the model and satellite observations of the total ozone column (TOC) for the 1980 2015 period at mid-latitudes. We show that the overall ozone response to VSLBr at mid-latitudes follows the stratospheric evolution of long-lived inorganic chlorine and bromine throughout the 21st century. Additional ozone loss due to VSLBr is maximized during the present-day period (1990 2010), with TOC differences of 8DU (3 %) and 5:5DU (2 %) for the Southern Hemisphere and Northern Hemisphere midlatitudes (SH-MLs and NH-MLs), respectively. Moreover, the projected TOC differences at the end of the 21st century are 50% lower than the values found for the present-day period. We find that seasonal VSLBr impact on lowermost stratospheric ozone at mid-latitude is influenced by the seasonality of the heterogeneous inorganic-chlorine reactivation processes on ice crystals. Indeed, due to the more efficient reactivation of chlorine reservoirs (mainly ClONO2 and HCl) within the colder SH-ML lowermost stratosphere, the seasonal VSLBr impact shows a small but persistent hemispheric asymmetry through the whole modelled period. Our results indicate that, although the overall VSLBr-driven ozone destruction is greatest during spring, the halogen-mediated (Halogx-Loss) ozone loss cycle in the mid-latitude lowermost stratosphere during winter is comparatively more efficient than the HOx cycle with respect to other seasons. Indeed, when VSLBr are considered, Halogx-Loss dominates wintertime lowermost stratospheric ozone loss at SH-MLs between 1985 and 2020, with a contribution of inter-halogen ClOx BrOx cycles to Halogx-Loss of 50 %. Within the tropics, a small (2:5 DU) and relatively constant (1 %) ozone depletion mediated by VSLBr is closely related to their fixed emissions throughout the modelled period. By including the VSLBr sources, the seasonal Halogx-Loss contribution to lowermost stratospheric ozone loss is practically dominated by the BrOx cycle, reflecting the low sensitivity of very short-lived (VSL) bromine to background halogen abundances to drive tropical stratospheric ozone depletion. We conclude that the link between biogenic bromine sources and seasonal changes in heterogeneous chlorine reactivation is a key feature for future projections of mid-latitude lowermost stratospheric ozone during the 21st century. ; This research has been supported by the European Research Council Executive Agency under the European Union's Horizon 2020 Research and Innovation programme (grant no. ERC-2016-COG 726349 CLIMAHAL) and the Agencia Nacional de Promoción Científica y Técnica (grant no. ANPCYT PICT-2016-0714).

This is an open access article under the terms of the Creative Commons Attribution-NonCommercial License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes. ; We have compiled and analyzed a comprehensive data set of field observations of iodine speciation in marine aerosol. The soluble iodine content of fine aerosol (PM1) is dominated by soluble organic iodine (SOI; ∼50%) and iodide (∼30%), while the coarse fraction is dominated by iodate (∼50%), with nonnegligible amounts of iodide (∼20%). The SOI fraction shows an equatorial maximum and minima coinciding with the ocean "deserts," which suggests a link between soluble iodine speciation in aerosol and ocean productivity. Among the major aerosol ions, organic anions and non-sea-salt sulfate show positive correlations with SOI in PM1. Alkali cations are positively correlated to iodate and negatively correlated with SOI and iodide in coarse aerosol. These relationships suggest that under acidic conditions iodate is reduced to HOI, which reacts with organic matter to form SOI, a possible source of iodide. In less acidic sea-salt or dust-rich coarse aerosols, HOI oxidation to iodate and reaction with organic matter likely compete. © 2022 The Authors. ; J. C. G. M. acknowledges financial support from the State Agency for Research of the Spanish MCIU through the "Center of Excellence Severo Ochoa" award to the Instituto de Astrofísica de Andalucía (SEV-2017-0709) and the Ramon y Cajal Program (RYC-2016-19570). A. S.-L. acknowledges financial support from the European Research Council Executive Agency under the European Union's Horizon 2020 Research and Innovation program (Project "ERC-2016-COG 726349 CLIMAHAL"). ; Peer reviewed

23 pags., 10 figs., 4 tabs. ; In this work, we describe the compilation and homogenization of an extensive data set of aerosol iodine field observations in the period between 1963 and 2018 and we discuss its spatial and temporal dependences by comparison with CAM-Chem model simulations. A close to linear relationship between soluble and total iodine in aerosol is found (∼80% aerosol iodine is soluble), which enables converting a large subset of measurements of soluble iodine into total iodine. The resulting data set shows a distinct latitudinal dependence, with an enhancement toward the Northern Hemisphere (NH) tropics and lower values toward the poles. This behavior, which has been predicted by atmospheric models to depend on the global distribution of the main oceanic iodine source (which in turn depends on the reaction of ozone with aqueous iodide on the sea water-air interface, generating gas-phase I2 and HOI), is confirmed here by field observations for the first time. Longitudinally, there is some indication of a waveone profile in the tropics, which peaks in the Atlantic and shows a minimum in the Pacific. New data from Antarctica show that the south polar seasonal variation of iodine in aerosol mirrors that observed previously in the Arctic, with two equinoctial maxima and the dominant maximum occurring in spring. While no clear seasonal variability is observed in NH middle latitudes, there is an indication of different seasonal cycles in the NH tropical Atlantic and Pacific. Long-term trends cannot be unambiguously established as a result of inhomogeneous time and spatial coverage and analytical methods ; Juan Carlos Gómez Martín acknowledges financial support from the State Agency for Research of the Spanish MCIU through the "Center of Excellence Severo Ochoa" award to the Instituto de Astrofísica de Andalucía (SEV-2017-0709) and the Ramon y Cajal Program (RYC-2016-19,570). Alfonso Saiz-Lopez acknowledges financial support from the European Research Council Executive Agency under the European Union's Horizon 2020 Research and Innovation program (Project "ERC-2016-COG 726349 CLIMAHAL"). Rafael P. Fernandez would like to thank financial support from ANPCyT (PICT 2015-0714), UNCuyo (SeCTyP M032/3853), and UTN (PID 4920-194/2018). ; Peer reviewed

17 pags., 9 figs., 1 tab. ; Ocean-going ships supply products from one region to another and contribute to the world's economy. Ship exhaust contains many air pollutants and results in significant changes in marine atmospheric composition. The role of reactive halogen species (RHS) in the troposphere has received increasing recognition and oceans are the largest contributors to their atmospheric burden. However, the impact of shipping emissions on RHS and that of RHS on ship-originated air pollutants have not been studied in detail. Here, an updated Weather Research Forecasting coupled with Chemistry model is utilized to explore the chemical interactions between ship emissions and oceanic RHS over the East Asia seas in summer. The emissions and resulting chemical transformations from shipping activities increase the level of NO and NO at the surface, increase O in the South China Sea, but decrease O in the East China Sea. Such changes in pollutants result in remarkable changes in the levels of RHS (>200% increase of chlorine; ∼30% and ∼5% decrease of bromine and iodine, respectively) as well as in their partitioning. The abundant RHS, in turn, reshape the loadings of air pollutants (∼20% decrease of NO and NO; ∼15% decrease of O) and those of the oxidants (>10% reduction of OH and HO; ∼40% decrease of NO) with marked patterns along the ship tracks. We, therefore, suggest that these important chemical interactions of ship-originated emissions with RHS should be considered in the environmental policy assessments of the role of shipping emissions in air quality and climate. ; This study received funding from the European Research Council Executive Agency under the European Union's Horizon 2020 Research and Innovation Program (Project ERC-2016- COG 726349 CLIMAHAL) and was supported by the Consejo Superior de Investigaciones Científicas (CSIC) of Spain and The Program for Professor of Special Appointment (Eastern Scholar) at Shanghai Institutions of Higher Learning and Shanghai Thousand Talents Program. The development and maintenance of the WRF-Chem model are conducted by NOAA/ESRL/GSD in active collaboration with other institutes. Computing resources, support, and data storage were provided by the Climate Simulation Laboratory at NCAR's Computational and Information Systems Laboratory (CISL), sponsored by the NSF. International cooperation between CSIC (Spain) and CONICET (Argentina) was supported by the i-COOP program (B20331). R.P.F. would like to thank ANPCyT (PICT 2015-0714), UNCuyo (SeCTyP M032/3853), and UTN (PID 4920-194/2018) for financial support. IITM is funded by the Ministry of Earth Sciences, Government of India.

11 pags., 6 figs. ; CH4 is the most abundant reactive greenhouse gas and a complete understanding of its atmospheric fate is needed to formulate mitigation policies. Current chemistry-climate models tend to underestimate the lifetime of CH4, suggesting uncertainties in its sources and sinks. Reactive halogens substantially perturb the budget of tropospheric OH, the main CH4 loss. However, such an effect of atmospheric halogens is not considered in existing climate projections of CH4 burden and radiative forcing. Here, we demonstrate that reactive halogen chemistry increases the global CH4 lifetime by 6–9% during the 21st century. This effect arises from significant halogen-mediated decrease, mainly by iodine and bromine, in OH-driven CH4 loss that surpasses the direct Cl-induced CH4 sink. This increase in CH4 lifetime helps to reduce the gap between models and observations and results in a greater burden and radiative forcing during this century. The increase in CH4 burden due to halogens (up to 700 Tg or 8% by 2100) is equivalent to the observed atmospheric CH4 growth during the last three to four decades. Notably, the halogen-driven enhancement in CH4 radiative forcing is 0.05 W/m2 at present and is projected to increase in the future (0.06 W/m2 by 2100); such enhancement equals ~10% of present-day CH4 radiative forcing and one-third of N2O radiative forcing, the third-largest well-mixed greenhouse gas. Both direct (Cl-driven) and indirect (via OH) impacts of halogens should be included in future CH4 projections. ; This study received funding from the European Research Council Executive Agency under the European Union's Horizon 2020 Research and Innovation Program (Project ERC-2016- COG 726349 CLIMAHAL to A.S.L.). The CESM project is supported primarily by the National Science Foundation (NSF). Some material in this publication is based upon work supported by the National Center for Atmospheric Research (NCAR), which is a major facility sponsored by the NSF under Cooperative Agreement 1852977. Computing ...

13 pags., 7 figs. ; Severe and persistent haze events in northern China, characterized by high loading of fine aerosol especially of secondary origin, negatively impact human health and the welfare of ecosystems. However, current knowledge cannot fully explain the formation of this haze pollution. Despite field observations of elevated levels of reactive halogen species (e.g., BrCl, ClNO, Cl, HBr) at several sites in China, the influence of halogens (particularly bromine) on haze pollution is largely unknown. Here, for the first time, we compile an emission inventory of anthropogenic bromine and quantify the collective impact of halogens on haze pollution in northern China. We utilize a regional model (WRF-Chem), revised to incorporate updated halogen chemistry and anthropogenic chlorine and bromine emissions and validated by measurements of atmospheric pollutants and halogens, to show that halogens enhance the loading of fine aerosol in northern China (on average by 21%) and especially its secondary components (∼130% for secondary organic aerosol and ∼20% for sulfate, nitrate, and ammonium aerosols). Such a significant increase is attributed to the enhancement of atmospheric oxidants (OH, HO, O, NO, Cl, and Br) by halogen chemistry, with a significant contribution from previously unconsidered bromine. These results show that higher recognition of the impact of anthropogenic halogens shall be given in haze pollution research and air quality regulation. ; This study received funding from the European Research Council Executive Agency under the European Union's Horizon 2020 Research and Innovation Programme (Project ERC-2016- COG 726349 CLIMAHAL) and the Hong Kong Research Grants Council (Project T24-504/17-N and APolyU502/16). CU team is funded by NSF AGS-1822664. X.F. acknowledges the financial support of the Scientific Research Start-up Funds from Tsinghua Shenzhen International Graduate School (QD2021015C). The development and maintenance of the WRF-Chem model are conducted by NOAA/ESRL/GSD in active collaboration with other institutes. Computing resources, support, and data storage were provided by the Climate Simulation Laboratory at NCAR's Computational and Information Systems Laboratory (CISL), sponsored by the NSF.

10 pags., 4 figs. ; Many Chemistry-Climate Models (CCMs) include a simplified treatment of brominated very short-lived (VSL) species by assuming CHBr as a surrogate for VSL. However, neglecting a comprehensive treatment of VSL in CCMs may yield an unrealistic representation of the associated impacts. Here, we use the Community Atmospheric Model with Chemistry (CAM-Chem) CCM to quantify the tropospheric and stratospheric changes between various VSL chemical approaches with increasing degrees of complexity (i.e., surrogate, explicit, and full). Our CAM-Chem results highlight the improved accuracy achieved by considering a detailed treatment of VSL photochemistry, including sea-salt aerosol dehalogenation and heterogeneous recycling on ice-crystals. Differences between the full and surrogate schemes maximize in the lowermost stratosphere and midlatitude free troposphere, resulting in a latitudinally dependent reduction of ∼1–7 DU in total ozone column and a ∼5%–15% decrease of the OH/HO ratio. We encourage all CCMs to include a complete chemical treatment of VSL in the troposphere and stratosphere. ; This study has been funded by the European Union's Horizon 2020 Re-search and Innovation program (Project 'ERC-2016-COG 726349 CLIMAHAL'), and supported by the Consejo Superior de Investigaciones Científicas of Spain. Computing resources and support are provided by the Computational and Information System Laboratory (CISL,2017). R. P. Fernandez would like to thank financial support from CONICET, ANPCyT (PICT 2015-0714), UNCuyo (SeCTyP M032/3853) and UTN (PID 4920-194/2018). NCAR is sponsored by NSF under grant number 1852977. R. J. Salawitch appreciates support from the NASA (grant ACMP 80NSSC19K0983). The authors thank two anonymous reviewers for their constructive comments

9 pags., 3 figs. ; Polar stratospheric ozone has decreased since the 1970s due to anthropogenic emissions of chlorofluorocarbons and halons, resulting in the formation of an ozone hole over Antarctica. The effects of the ozone hole and the associated increase in incoming UV radiation on terrestrial and marine ecosystems are well established; however, the impact on geochemical cycles of ice photoactive elements, such as iodine, remains mostly unexplored. Here, we present the first iodine record from the inner Antarctic Plateau (Dome C) that covers approximately the last 212 years (1800-2012 CE). Our results show that the iodine concentration in ice remained constant during the pre-ozone hole period (1800-1974 CE) but has declined twofold since the onset of the ozone hole era (~1975 CE), closely tracking the total ozone evolution over Antarctica. Based on ice core observations, laboratory measurements and chemistry-climate model simulations, we propose that the iodine decrease since ~1975 is caused by enhanced iodine re-emission from snowpack due to the ozone hole-driven increase in UV radiation reaching the Antarctic Plateau. These findings suggest the potential for ice core iodine records from the inner Antarctic Plateau to be as an archive for past stratospheric ozone trends. ; This project received funding from the European Union's Horizon 2020 Research and Innovation program under grant agreement no. 689443 via project iCUPE (Integrative and Comprehensive Understanding on Polar Environments), part of the European Commission (ERA-PLANET) and by the "Programma Nazionale per la Ricerca in Antartide" (PNRA, project number PNRA16_00295). This study also received funding from the European Research Council Executive Agency under the European Union's Horizon 2020 Research and Innovation programme (Project 'ERC-2016-COG 726349 CLIMAHAL'). NCAR is sponsored by the National Science Foundation under Grant Number 1852977. R.P.F. would like to express thanks for the financial support from CONICET-UNCuyo (SIIP-06/M111) and ANPCyT (PICT 2015-0714). This research was also supported by the Korea Polar Research Institute (KOPRI) project (PE20030) and by the Grant to Department of Science, Roma Tre University (MIUR-Italy Dipartimenti di Eccellenza)

30 pags., 11 figs., 5 tabs. ; We quantify the stratospheric injection of brominated very short-lived substances (VSLS) based on aircraft observations acquired in winter 2014 above the Tropical Western Pacific during the CONvective TRansport of Active Species in the Tropics (CONTRAST) and the Airborne Tropical TRopopause EXperiment (ATTREX) campaigns. The overall contribution of VSLS to stratospheric bromine was determined to be 5.0 ± 2.1 ppt, in agreement with the 5 ± 3 ppt estimate provided in the 2014 World Meteorological Organization (WMO) Ozone Assessment report (WMO 2014), but with lower uncertainty. Measurements of organic bromine compounds, including VSLS, were analyzed using CFC-11 as a reference stratospheric tracer. From this analysis, 2.9 ± 0.6 ppt of bromine enters the stratosphere via organic source gas injection of VSLS. This value is two times the mean bromine content of VSLS measured at the tropical tropopause, for regions outside of the Tropical Western Pacific, summarized in WMO 2014. A photochemical box model, constrained to CONTRAST observations, was used to estimate inorganic bromine from measurements of BrO collected by two instruments. The analysis indicates that 2.1 ± 2.1 ppt of bromine enters the stratosphere via inorganic product gas injection. We also examine the representation of brominated VSLS within 14 global models that participated in the Chemistry-Climate Model Initiative. The representation of stratospheric bromine in these models generally lies within the range of our empirical estimate. Models that include explicit representations of VSLS compare better with bromine observations in the lower stratosphere than models that utilize longer-lived chemicals as a surrogate for VSLS. ; The CONTRAST field deployment was supported by the U.S. NSF, and the ATTREX field deployment was supported by the National Aeronautics and Space Administration (NASA). P. A. W., R. J. S., T. P. C., J. M. N., and D. C. A. received support from NSF, NASA Atmospheric Composition Modeling and Analysis Program (ACMAP), and the NASA Modeling, Analysis, and Prediction (MAP). D. C. A. also received support from the NASA Upper Atmospheric Research Program. J. M. N. was also supported by the NASA Postdoctoral Program at the NASA Goddard Space Flight Center, administered by Universities Space Research Association under contract with NASA. R. V. acknowledges funding from NSF awards AGS‐1261740 and AGS‐1620530. CONTRAST data are publicly available at "http://data.eol.ucar.edu/master_list/?project= CONTRAST." ATTREX data are publicly available at "https://espoarchive.nasa.gov/archive/browse/attrex/id4/GHawk." The National Center for Environmental Prediction (NCEP) meteorological data are available at "https://doi.org/10.5065/D6M043C6." CCMI outputs from CESM1‐WACCM and CESM1‐CAM4Chem are archived by the National Center for Atmospheric Research (NCAR) at "www.earthsystemgrid.org," and NCAR is sponsored by NSF. CCMI output from the EMAC‐L90MA‐SD simulation is available at "https://doi.org/10.5281/zenodo.1204495." All other CCMI simulations are archived by the British Atmospheric Data Centre at "http://badc.nerc.ac.uk/". Output from CAM‐chem‐SD is available as "NCAR/ACD CAMChem 1 Degree Forecast" at "http://catalog.eol.ucar.edu/contrast/model/CAMChem_NCAR_1deg/." WACCM and CAM‐Chem are components of the Community Earth System Model (CESM), which is also supported by NSF. Computing resources were provided by NCAR's Climate Simulation Laboratory, sponsored by NSF and other agencies. This research was enabled by the computational and storage resources of NCAR's Computational and Information System Laboratory (CISL). R. S. and K. A. S., with ACCESS‐CCM, acknowledge support from Australian Research Council's Centre of Excellence for Climate System Science (CE110001028), the Australian Government's National Computational Merit Allocation Scheme (q90), and Australian Antarctic science grant program (FoRCES 4012). CCSRNIES research was supported by the Environment Research and Technology Development Fund (2‐1303 and 2‐1709) of the Ministry of the Environment, Japan, and computations were performed on NEC‐SX9/A(ECO) computers at the CGER, NIES. The EMAC simulations have been performed at the German Climate Computing Centre (DKRZ) through support from the Bundesministerium für Bildung und Forschung (BMBF). DKRZ and its scientific steering committee are gratefully acknowledged for providing the HPC and data archiving resources for the consortial project ESCiMo (Earth System Chemistry integrated Modelling). The TOMCAT modeling was supported by NERC NCAS and the SISLAC project (NE/R001782/1), and the simulations were performed on the Archer and Leeds HPC Systems.